US4927553A - Haze-free boronated antioxidant - Google Patents
Haze-free boronated antioxidant Download PDFInfo
- Publication number
- US4927553A US4927553A US06/492,354 US49235483A US4927553A US 4927553 A US4927553 A US 4927553A US 49235483 A US49235483 A US 49235483A US 4927553 A US4927553 A US 4927553A
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- boronated
- butyl
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/062—Cyclic esters
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/063—Complexes of boron halides
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
Definitions
- This invention relates to boronated phenolic antioxidants, coadditives, and haze-forming problems solved by coadditives.
- This invention relates in particular to the prevention and/or correction of a haze or film in a boronated phenolic antioxidant and organic materials containing the same with certain hydrocarbon diols.
- boronated phenolics are well known in the art, including large molecular phenolics incorporating the moiety, 2,6- di-tert-butylphenol and the like.
- Various hydrocarbon diols are generally known in the chemical arts for various purposes.
- boric acid means generally the compound B(OH) 3 (or H 3 BO 3 ) but should also be interpreted to include related hydrolysis products which may be produced in the manner of boric acid or along with boric acid depending upon the antioxidant used and which present themselves as a haze or film subject to being cured by the present invention.
- the invention is a hydrolytically stable additive composition
- a boronated phenolic antioxidant and a diol member selected from the group consisting of:
- tertiary amine diols having attached to the nitrogen atom one fatty alkyl group of twelve to eighteen carbon atoms and either two or more polyoxyethylene groups or two 2-hydroxyethyl groups.
- the invention is also a hyrolytically stable additive composition
- the invention is also organic material normally susceptible to gradual degradation in the presence of oxygen, containing an antioxidant amount of a boronated phenolic antioxidant subject to hydrolysis in the presence of moisture so as to produce boric acid appearing as a haze and a hydrocarbon diol soluble in the organic material and reactive with the boric acid to form a stable ring compound soluble in the organic material.
- a preferred embodiment of this invention is a boronated phenolic antioxidant having improved hydrolytic stability and being made haze-free/film-free by incorporation into the antioxidant of about 0.5-25 weight percent of a diol reactive with boric acid to form a stable five-member ring of structure III: ##STR3## where R 1 , R 2 , R 3 , and R 4 are independently selected alkyl, cycloalkyl, aryl, aralkyl, or alkaryl, R 1 , R 2 , R 3 , and R 4 are preferably alkyl, more preferably methyl.
- Suitable substituents for the R groups are methyl, ethyl, propyl, tert-butyl, sec-butyl, and the like; cyclopentyl, cyclohexyl, cyclooctyl, and the like; phenyl, benzyl, and the like.
- the reaction mechanism to form such products is believed to be: ##STR4##
- any two of the "R" groups in the diol of structure I may together form a ring, with or without one or both of the carbon atoms in structure I.
- 1,2-dimethyl-1,2-cyclohexanediol is suitable since R 1 and R 4 are methyl, and R 2 and R 3 together with both carbons form a saturated cyclohexane ring.
- suitable are compounds where only one of the carbon atoms is incorporated into the ring and where neither carbon atom is incorporated but two or more R's form an aromatic ring.
- a diol is suitable, even where R 1 and R 2 may together form a ring and similarly for R 3 and R 4 or R 1 and R 3 .
- R 1 and R 2 may together form a ring and similarly for R 3 and R 4 or R 1 and R 3 .
- diols having all R substituents other than H are effective.
- the R's are alkyls, more preferably methyls. This supports the formation of stable ring structures.
- open chain hydrocarbon diols are effective if the ring structure of the boric acid reaction product is stabilized by substituents.
- cyclic hydrocarbon diols with the hydroxyl groups on adjacent carbon atoms should preferably have the hydroxy groups on the same side of the ring which may be called “cis” as opposed to “trans” for hydroxy groups on spatially opposite sides of the plane of the ring.
- a preferred ketone is acetone.
- Other suitable ketones include methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and methyl cyclohexyl ketone. Electrochemical reduction is also suitable.
- Suitable coupling agents are sodium, sodium amalgam, aluminum amalgam, magnesium, other metals, and various reductive coupling agents known in the art.
- Pinacol which may be formed by the reductive coupling of acetone is the most preferred diol hydrocarbon of the invention.
- Another highly preferred diol is pinane diol which has two hydroxy groups locked into a cis position as explained above.
- the cis-pinane diol may be prepared by oxidation of alpha pinene with agents like trimethylamine oxide dihydrate using a catalyst, for example oxmium tetroxide.
- Another class of preferred hydrocarbon diols are the tertiary amine diols having attached to the nitrogen atom one fatty alkyl group of twelve to eighteen carbon atoms and either two or more polyoxyethylene groups or two 2-hydroxyethyl groups.
- Highly preferred are the cocoamines (twelve carbon alkyl group), such as bis(2-hydroxyethyl)cocoamine and polyoxyethylene (5) cocoamine.
- These two diols are available commercially from Armak Company as Ethomeen® C/12 and C/15 polyethoxylated amines, respectively.
- Other suitable tertiary amine diols are described in the Armak Company 1975 booklet, Chemicals for Industry.
- the boronated phenolics of the invention are diverse. They include but are not limited to products obtained by reaction between a hindered phenolic compound and a completely esterified symmetrical oxy acid of boron whose esterifying radicals are derived from a monohydric alcohol and having discrete monovalent hydrocarbon ester groups.
- the dinuclear phenolics used to obtain these reaction products include 1,1-bis-(3,5-di-tert-butyl-4-hydroxphenyl)methane; 1,1-bis-(2-hydroxy-3-tert-butyl-5-methylphenyl)methane; 1,1-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)phenylmethane; 3,3'-di-(1-ethylallyl)4,4'-di-hydroxydiphenyl; 1,10-di-(3-sec-amyl-2-hydroxyphenyl)octadecane; 2,2'-bis-[3-(1-phenyl-1-ethyl)-4-hydroxyphenyl]propane; 4,4'-isopropylidene-di-(2-isopropylphenyl); 3,5,5'-tridodecyl-3'-ethyl-4,4'-dihydroxydipheny
- the boron esters used to obtain these products include isopropyl metaborate, hexyl metaborate trimer, 2-ethoxy-ethyl metaborate trimer, tri-sec-butyl orthoborate, tri-n-hexyl orthoborate, diethylphenyl boronate, n-butyl-di-p-tolylborinate, tetra-n-hexyl pyroborate, methyl metaborate trimer, n-butyl polyborate, isopropyl metaborate trimer, n-butyl metaborate, methyl di-n-butylborinate, dibutyl dodecyl orthoborate, and many others.
- the boronated phenolics of the invention also include the boron esters derived from boron acids selected from the group pyroboric, boronic, and borinic acids wherein an esterifying group is an alkylphenol.
- boron esters derived from boron acids selected from the group pyroboric, boronic, and borinic acids wherein an esterifying group is an alkylphenol.
- These include tri-(2,6-di-tert-butylphenyl)orthoborate; tri-(2,6-di-tert-amylphenyl)orthoborate; di-(2,6-di-tert-amylphenyl)monoether orthoborate; mono-(2,6-di-tert-butylphenyl)dibutyl orthoborate; mono-(2,6-di-tert-butylphenyl)ethylene glycol orthoborate; tri-(2,6-di-tert
- These compounds may be prepared from (1) phenolics including 2,6-di-tert-butylphenol; methylenebis-(2,6-di-tert-butylphenol); 2-tert-butyl-6-tert-amylphenol; 2,6-diamylphenol; 1,1-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)methane; and the like; and (2) boron compounds including tri-n-butyl orthoborate; orthoboric acid; bis-(1,1,3-trimethyltrimethylene)pyroborate; isopropyl-(2-methyl-2,4-pentylene)orthoborate; metaboric acid; isopropyl metaborate; butyl borinic acid; dibutyl monochloroborinate; tetraalkylpyroborates; isopropylmetaborate trimer, and the like.
- phenolics including 2,6-di-tert-butylphenol;
- the boronated products of the invention include borate esters of wax alkylated phenol, wax alkylated naphthol, wax alkylated cresol, cetylphenol, octadecylphenol, di-tert-octylphenol, isohexadecylphenol, and C 16-20 branched chain alkylpehnols. These esters are usually obtained by reaction with boric acid.
- 2,6-dialkyl alkylphenyl dialkyl borates such as 2,6-di-tert-butylphenyl-di-n-butyl orthoborate.
- Additional boronated phenolics aided by the coadditives detailed below include the borates disclosed by Washburn et al. in U.S. Pat. No. 3,347,793 and by Hunter et. al. in U.S. Pat. No. 3,359,298, which are hereby incorporated herein by reference in their entirety.
- the boronated phenolics of U.S. Pat. Application Ser. No. 360,781, filed Mar. 22, 1982 are highly preferred antioxidants of this invention.
- the most highly preferred boronated phenolic is one having about 0-50 weight percent 4,4'-methylenebis(2,6-di-tert-butylphenol), about 25-75 weight percent 4,4'-methylenebis(2,6-di-tert-butylphenol)mono(di-sec-butyl orthoborate), and about 10-75 weight percent 4,4'-methylenebis(2,6-di-tert-butylphenol)-di-(di-sec-butyl orthoborate).
- the most highly preferred boronated phenolic antioxidants protected by the diols of the invention may be prepared by a process comprising reacting at elevated temperature (a) one mole part of 4,4'-methylenebis(2,6-di-tert-butylphenol) and (b) 0.5-5.0 mole parts of a tri-sec-alkyl orthoborate wherein the sec-alkyl group contains 4-12 carbon atoms.
- the mole ratio of tri-sec-alkyl orthoborate to 4,4'-methylenebis-(2,6-di-tert-butyl phenol) can vary over a wide range.
- a useful range is about 0.5-6 moles of tri-sec-alkyl orthoborate per mole of 4,4'-methylene-bis-(2,6-di-tert-butylphenol.
- a more preferred range is about 1-3 to 1.
- the antioxidants are made by forming a reaction mixture of the tri-sec-alkyl orthoborate and 4,4'-methylenebis-(2,6-di-tert-butyl phenol) and heating this mixture while distilling out displaced sec-alkanol.
- the reaction should be conducted at a temperature high enough to cause the phenol hydroxyl to displace a sec-alkyl group from the orthoborate ester and to cause the displaced sec-alcohol to distill out but not so high as to cause decomposition of the reactants or products.
- a useful temperature range in which to experiment is from about 150-300° C. When using tri-sec-butyl orthoborate, the preferred temperature range is about 200-275° C.
- the transesterification reaction can be catalyzed by a small amount of an acidic material.
- an acidic material This include sulfuric acid, phosphoric acid, methane sulfonic acid, p-toluene sulfonic acid, and the like.
- the preferred catalysts are the lower fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, and the like. The most preferred catalyst is acetic acid.
- a useful catalyst range is about 0.02-0.2 weight percent based upon total reaction mass.
- the principal components in the reaction mixture are 4,4'-methylene-bis-(2,6-di-tert-butyl phenol) mono-(di-sec-C 4-12 alkyl orthoborate) ester and 4,4'-methylenebis-(2,6-di-tert-butyl phenol) di-(di-sec-C 4-12 alkyl orthoborate) ester together with varied amounts of unreacted 4,4'-methylene-bis-(2,6-di-tert-butyl phenol).
- ZDDP zinc dialkyldithiophosphate
- the amount of ZDDP in crankcase lubricating oil formulated for use to in the crankcase of an internal combustion engine is reduced to a level which provides a low phosphorus lubricating oil composition containing only about 0.05-0.11 weight percent phosphorus.
- the low phosphorus formulation is made possible by including in the oil an antioxidant amount of the previously-described reaction product of 4,4'-methylenebis-(2,6-di-tert-butyl phenol) and a tri-sec-C 4 - 12 alkyl orthoborate.
- the most preferred additive is the reaction product of 4,4'-methylene-bis-(2,6-di-tert-butyl phenol) and tri-sec-butyl) orthoborate.
- the product was further analyzed using high pressure liquid chromatography (HPLC) and found to contain 18 weight percent 4,4'-MBTP, 51 weight percent mono-(di-sec-butyl orthoborate) ester of 4,4'-MBTP and 24 weight percent di-(di-sec-butyl orthoborate) ester of 4,4'-MBTP. The remaining components were not identified.
- the product contained 1.4 weight percent boron and analyzed by HPLC to contain 29 weight percent 4,4'-MBTP, 52 weight percent mono-(di-sec-butyl orthoborate) ester of 4,4'-MBTP and 20 weight percent di-(di-sec-butyl orthoborate) ester of 4,4'-MBTP.
- reaction time was reduced to two hours while heating from 200° to 260° C.
- the incompatible diols include 1,2-butanediol; 1,2-octanediol; 2-ethyl-2-methyl-1,3-propanediol; 1,2-cyclohexanediol (trans); 1,3-cyclohexanediol; 1,3-butanediol; 1,4-butanediol; 2,5-hexanediol; 1,10-decanediol.
- some of these diols may be compatible and effective with other neat antioxidants or compositions of organic material containing the antioxidant.
- the haze formed in boronated phenolic antioxidants can interfere with product handling.
- the haze/film can interfere with product handling and/or incorporation of the boronated phenolic into a substrate material such as lubricating oil.
- the invention assists handling, permits long-term storage, and facilitates mixing of the boronated phenolic into an organic material substrate. For example, if a finished oil becomes cloudy, oil passageways and filters could become blocked leading to loss of lubrication.
- the diols preventing haze/film may be incorporated into the boronated phenolics by various methods of mixing including the use of impellers or rotating mixing chambers.
- the diol is added in an amount effective to prevent formation of haze/film, depending upon the particular boronated phenolic and the diol selected.
- a suitable range is about 0.5 to 25 weight percent diol.
- glycols and diols are ineffective because either they are not soluble in the antioxidant-protected substrate or they do not combine with boric acid hydrolysis product to form a stable complex/compound which does not itself form a haze or sediment.
- the diols of the invention may not be soluble in the boronated phenolic antioxidant but they must be capable of so mixing with the antioxidant that haze is prevented/corrected.
- the diol In an organic material protected by the boronated phenolic antioxidant the diol must prevent-correct the haze from the hydrolysis product so as to form a complex or compound which does not itself appear as a haze, film, or sediment. More preferably, the compound or complex formed is soluble in the organic material.
- Lubricating oils are a preferred class or organic materials protected by the invention.
- the substrate organic materials protected by the haze-free boronated phenolics of the invention are those normally subject to gradual degradation in the presence of oxygen during use over an extended period.
- the organic compositions protected by the present haze-free antioxidants are the type in which the art recognizes the need for antioxidant protection and to which an antioxidant of some type is customarily added to obtain an extended service life.
- the oxidative degradation protected against is the slow gradual deterioration of the organic composition rather than, for example, combustion.
- the present haze-free antioxidants are not flame retarding additives or flame suppressing additives and the degradation protected against is not combustion but rather the gradual deterioration of the organic composition due to the effects of oxygen over an extended period of time.
- organic materials in which the additives are useful include polymers, both homopolymers and copolymers, of olefinically unsaturated monomers, for example, polyolefins such as polyethylene, polypropylene, polybutadiene, and the like. Also, polyhalohydrocarbons such as polyvinyl chloride, polychloroprene, polyvinylidene chloride, polyfluoro olefins, and the like, are afforded stabilization.
- the additives provide antioxidant protection in natural and synthetic rubbers such as copolymers of olefinically unsaturated monomers including styrene-butadiene rubber (SBR rubber), ethylene-propylene copolymers, ethylene-propylene-diene terpolynmers such as the terpolymer of ethylene, propylene and cyclopentadiene or 1,4-cyclooctadiene, Polybutadiene rubbers such as cis-polybuta diene rubber are protected. Poly-2-chloro-1,3-butadiene (neoprene) and poly-2-methyl-1,3-butadiene (isoprene rubber) are stabilized by the present additives.
- SBR rubber styrene-butadiene rubber
- ethylene-propylene copolymers ethylene-propylene copolymers
- ethylene-propylene-diene terpolynmers such as the terpolymer of ethylene,
- ABS resins are effectively stabilized.
- Ethylene vinyl acetate copolymers are protected, as are butenemethacrylate copolymers.
- Nitrogen-containing polymers such as polyurethanes, nitrile rubber, and lauryl acrylate-vinylpyrrolidone copolymers are effectively stabilized.
- Adhesive compositions such as solutions of polychloroprene (neoprene) in toluene are protected.
- Fats and oils of animal and vegetable origin are protected against gradual deterioration. Examples of these are lard, beef tallow, coconut oil, safflower oil, castor oil, babassu oil, cottonseed oil, corn oil, rapeseed oil, tall oil and the like.
- Petroleum oils and waxes such as solvent-refined mid-continent lubricating oil microcrystalline wax, and Gulf-coast lubricating oils are effectively stabilized.
- Vitamin extracts especially the fat-soluble vitamins such as Vitamin A, B, D, E and C, are effectively stabilized against degradation.
- the additives are useful in foamed plastics such as expanded polystyrene, polyurethane foams, and the various foamed rubbers, alkyd resins such as short oil terephthalic acid-glycerol-linseed oil resins, and typical long oil resins of trimellitic acid-clycol-tung oil resins including epoxidemodified alkyd resins.
- alkyd resins such as short oil terephthalic acid-glycerol-linseed oil resins
- typical long oil resins of trimellitic acid-clycol-tung oil resins including epoxidemodified alkyd resins.
- Epoxy resins themselves such as isopropylidenebisphenolepichlorohydrin epoxy resins are stabilized against degradation.
- Hydrocarbons such as gasoline, kerosene, diesel fuel, fuel oil, furnace oil, and jet fuel are effectively protected.
- synthetic hydrocarbon lubricants for example ⁇ -decene trimer, polybutene lubricants di- and tri-C 12 - 30 alkylated benzene and naphthalene synthetic lubricants are likewise protected.
- Organometallics such as tetraethyllead, tetramethyllead, tetravinyllead, ferrocene, methyl ferrocene, cyclopentadienyl manganese tricarbonyl, methyl cyclopentadienyl manganese tricarbonyl, cyclopentadienyl nickel nitrosyl, and the like, are effectively protected against oxidative degradation. Silicone oils and greases are also protected.
- Synthetic ester lubricants such as those used in turbines and turbojet engines are given a high degree of stabilization.
- Typical synthetic ester lubricants include di-2-ethylhexyl sebacate, trimethylolpropane tripelargonate, C 5 - 9 aliphatic monocarboxylic esters of pentaerythritol, complex esters formed by condensing under esterifying conditions, mixtures of polyols, polycarboxylic acids, and aliphatic monocarboxylic acids and/or monohydric alkanols.
- Polyamides such as adipic acid-1,6-diaminohexane condensates and poly-6-aminohexanoic acid (nylon) are effectively stabilized.
- Polyalkylene oxides such as copolymers of phenol with ethylene oxide or propylene oxide are stabilized.
- Polyphenyl ethers such as poly-2,6-dimethylphenyl ether formed by polymerization of 2,6-dimethylphenol using a copper-pyridine catalyst are stabilized.
- Polycarbonate plastics and other polyformaldehydes are also protected.
- Linear polyesters such as phthalic anhydride-glycol condensates are given a high degree of protection. Other polyesters such as trimellitic acid-glycerol condensates are also protected.
- Polyacrylates such as polymethacrylate and polymethylmethacrylate are effectively stabilized. Polyacrylonitriles and copolymers of acrylonitriles with other olefinically unsaturated monomers such as methylmethacrylates are also effectively stabilized.
- Polyurethanes formed from diisocyanates e.g. toluene diisocyanate
- polyols and optionally polyamine modifiers are likewise protected against oxidative degradation.
- the additives can be used to protect any of the many organic substrate to which an antioxidant is normally added. It can be used where economics permit to protect such substrates as asphalt, paper, flurocarbons, such as teflon, polyvinyl acetate, polyvinylidene chloride, coumaroneindene resins, polyvinyl ethers, polyvinylidene bromide, polyvinyl bromide, acrylonitrilevinyl bromide copolymer, vinyl butural resins, silicones such as dimethylsilicone lubricants, phosphate lubricants such as tricresylphosphate, and the like.
- flurocarbons such as teflon
- polyvinyl acetate polyvinylidene chloride
- coumaroneindene resins polyvinyl ethers
- polyvinylidene bromide polyvinyl bromide
- acrylonitrilevinyl bromide copolymer vinyl butural
- the additives are incorporated into the organic substrate in a small but effective amount so as to provide the required antioxidant protection.
- a useful range is from about 0.005 to about 10 weight percent, and a preferred range is from about 0.05 to 5 weight percent.
- the additive can be merely mixed into the substrate.
- the organic substrate is in solution and the additive is added to the solution and the solvent removed.
- Solid organic substrates can be merely sprayed with a solution of the additive in a volatile solvent.
- stabilized grain products result from spraying the grain with a toluene solution of the additive.
- the additive can be added following the polymerization stage by mixing it with the final emulsion or solution polymerization mixture and then coagulating or removing solvent to recover the stabilized polymer. It can also be added at the compounding stage by merely mixing the additive with the rubbery polymer in commercial mixing equipment such as a Banbury blender.
- rubbery polymers such as styrene-butadiene rubber, cispolybutadiene or isoprene polymers are blended with the antioxidant together with the other ingredients normally added such as carbon black, oil, sulfur, zinc oxide, stearic acid, vulcanization accelerators, and the like.
- the resultant mixture is fabricated and molded into a finished form and vulcanized.
- the additives are especially useful in mineral oil or in synthetic oils of viscosity suitable for use in the crankcase of an internal combustion engine.
- Crankcase lubricating oils have a viscosity up to about 80 SUS at 210° F.
- motor oils are given a classification of both 0° and 210° F., such as SAE 10W 40 or SAE 5W 30.
- Mineral oils include those of suitable viscosity refined from crude oil from all sources including Gulfcoast, midcontinent, Pennsylvania, California, Alaska, North Sea, and the like. Various standard refinery operations can be used in processing the mineral oil.
- Synthetic oil includes both hydrocarbon synthetic oil and synthetic esters.
- Useful synthetic hydrocarbon oils include liquid polymers of ⁇ -olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6-12 ⁇ -olefins such as ⁇ -decene trimer. Likewise, alkylbenzenes of proper viscosity can be used, such as didodecylbenzene.
- Useful synthetic esters include the esters of both monocarboxylic acid and polycarboxylic acid as well as monohydroxy alkanols and polyols. Typical examples are didodecyl adipate, trimethylol propane tripelargonate, pentaerythritol tetracaproate, di-(2-ethylhexyl) adipate, dilauryl sebacate and the like. Complex esters prepared from mixtures of mono- and dicarboxylic acid and mono- and polyhydroxyl alkanols can also be used.
- Blends of mineral oil with synthetic oil are particularly useful. For example, blends of 5-25 weight percent hydrogenated ⁇ -decene trimer with 75-95 weight percent 150 SUS (100° F.) mineral oil results in an excellent lubricant. Likewise, blends of about 5-25 weight percent di-(2-ethylhexyl) adipate with mineral oil of proper viscosity results in a superior lubricating oil. Also blends of synthetic hydrocarbon oil with synthetic esters can be used. Blends of mineral oil with synthetic oil are especially useful when preparing low viscosity oil (e.g. SAE 5W 20) since they permit these low viscosities without contributing excessive volatility.
- low viscosity oil e.g. SAE 5W 20
- the more preferred lubricating oil composition includes zinc dihydrocarbyldithiophosphate (ZDDP) in combination with the present additives.
- ZDDP zinc dihydrocarbyldithiophosphate
- Both zinc dialkyldithiophosphates and zinc dialkaryldithiophosphates as well as mixed alkyl-aryl ZDDP are useful.
- a typical alkyl-type ZDDP contains a mixture of isobutyl and isoamyl groups.
- Zinc di-(nonylphenyl)dithiophosphate is a typical aryl-type ZDDP.
- the amount of ZDDP used has imparted as much as 0.14 weight percent or more phosphorus to the oil which can damage exhaust gas catalysts. With the use of the present additives, the amount of ZDDP can be reduced to supply less than 0.11 weight percent phosphorus to the oil.
- alkaline earth metal petroleum sulfonates or alkaline earth metal alkaryl sulfonates are the alkaline earth metal petroleum sulfonates or alkaline earth metal alkaryl sulfonates.
- examples of these are calcium petroleum sulfonates, magnesium petroleum sulfonates, barium alkaryl sulfonates, calcium alkaryl sulfonates or magnesium alkaryl sulfonates.
- Both the neutral and the overbased sulfonates having base numbers up to about 400 can be beneficially used. These are used in an amount to provide about 0.05-1.5 weight percent alkaline earth metal and more preferably about 0.1-1.0 weight percent.
- the lubricating oil composition contains a calcium petroleum sulfonate or alkaryl (e.g. alkylbenzene) sulfonate.
- Viscosity index improvers can be included such as the polyalkyl-methacrylate type or the ethylene-propylene copolymer type. Likewise, styrene-diene VI improvers or styrene-acrylate copolymers can be used. Alkaline earth metal salts of phosphosulfurized polyisobutyene are useful.
- crankcase oils can also contain ashless dispersants such as the polyolefin-substituted succinamides and succinimides of ethylene polyamines such as t etraethylenepentamine.
- the polyolefin succinic substituent is preferably a polyisobutene group having a molecular weight of from about 800 to 5000.
- Such ashless dispersants are more fully described in U.S. Pat. No. 3,171,892 and U.S. Pat. No. 3,219,666 incorporated herein by reference.
- ashless dispersants are the polyolefin succinic esters of mono- and polyhydroxyl alcohols containing 1 to about 40 carbon atoms. Such dispersants are described in U.S. Pat. No. 3,381,022 and U.S. Pat. No. 3,522,179.
- mixed ester/amides of polyolefin substituted succinic acid made using alkanols, amines and/or aminoalkanols represent a useful class of ashless dispersants.
- the succinic amide, imide and/or ester type ashless dispersants may be boronated by reaction with a boron compound such as boric acid.
- the succinic amide, imide and/or ester may be oxyalkylated by reaction with an alkylene oxide such as ethylene oxide or propylene oxide.
- ashless dispersants include the Mannich condensation products of polyolefin-substituted phenols, formaldehyde and polyethylene polyamine.
- the polyolefin phenol is a polyisobutylene-substituted phenol in which the polyisobutylene group has a molecular weight of from about 800 to 5000.
- the preferred polyethylene polyamine is tetraethylene pentamine.
- the above Mannich dispersants react with boric acid to form boronated dispersants having improved corrosion properties.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
TABLE 1 ______________________________________ Anti-Haze Effect of Diols Concentration* Diol Weight % Effect ______________________________________ None -- Haze within one day Pinacol 5 Slightly cloudy within 17 days " 10 Clear after 10 weeks Ethomeen ® C/12 5 Surface skin formed tertiary amine after 10 days (diol) Ethomeen ® C/12 10 Surface skin after tertiary amine several weeks (diol) **Ethomeen ® C/12 5 Heavy cloudiness C/15 tertiary after 17 days amine (diol) **Ethomeen ® 10 Somewhat cloudy C/15 tertiary after 26 days amine (diol) Pinane diol 10 Cloudy after 31 days ______________________________________ *Relative to boronated phenolic antioxidant **A pink coloration was observed on mixing.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US06/492,354 US4927553A (en) | 1983-05-06 | 1983-05-06 | Haze-free boronated antioxidant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US06/492,354 US4927553A (en) | 1983-05-06 | 1983-05-06 | Haze-free boronated antioxidant |
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US4927553A true US4927553A (en) | 1990-05-22 |
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US06/492,354 Expired - Fee Related US4927553A (en) | 1983-05-06 | 1983-05-06 | Haze-free boronated antioxidant |
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US (1) | US4927553A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5160650A (en) * | 1989-09-27 | 1992-11-03 | Chevron Research And Technology Company | Monoalkylamine complexes of borated higher carbon number alkyl catechols and lubricating oil compositions containing the same |
US5160652A (en) * | 1989-09-15 | 1992-11-03 | Chevron Research And Technology Company | Dialkylamine complexes of borated higher carbon number alkyl catechols and lubricating oil compositions containing the same |
US5160651A (en) * | 1989-09-15 | 1992-11-03 | Chevron Research And Technology Company | Trialkylamine complexes of borated higher carbon number alkyl catechols and lubricating oil compositions containing the same |
US5595964A (en) * | 1994-03-24 | 1997-01-21 | The Lubrizol Corporation | Ashless, low phosphorus lubricant |
US6140457A (en) * | 1999-02-26 | 2000-10-31 | General Electric Company | Static-resistant polycarbonates having DI-t-alkylphenyl end groups |
US6680349B2 (en) * | 2000-08-31 | 2004-01-20 | Masao Sumita | Organohybrid-based damping material, method for producing the same, and damping improver for damping material |
US20080318814A1 (en) * | 2006-01-13 | 2008-12-25 | Albemarle Corporation | Lubricant Oil and Lubricating Oil Additive Concentrate Compositions |
CN100575394C (en) * | 2007-04-27 | 2009-12-30 | 西安交通大学 | A kind of preparation method of hyper branched boric acid ester |
US20100286004A1 (en) * | 2006-03-29 | 2010-11-11 | Albemarle Corporation | Lubricant oil additive compositions |
CN105503535A (en) * | 2015-08-03 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Mixed base catalyst catalysis-based bisphenol anti-oxidant preparation method and use |
CN110591790A (en) * | 2019-07-23 | 2019-12-20 | 青岛博士德润滑科技有限公司 | Preparation method of environment-friendly copper corrosion inhibitor |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5160652A (en) * | 1989-09-15 | 1992-11-03 | Chevron Research And Technology Company | Dialkylamine complexes of borated higher carbon number alkyl catechols and lubricating oil compositions containing the same |
US5160651A (en) * | 1989-09-15 | 1992-11-03 | Chevron Research And Technology Company | Trialkylamine complexes of borated higher carbon number alkyl catechols and lubricating oil compositions containing the same |
US5160650A (en) * | 1989-09-27 | 1992-11-03 | Chevron Research And Technology Company | Monoalkylamine complexes of borated higher carbon number alkyl catechols and lubricating oil compositions containing the same |
US5595964A (en) * | 1994-03-24 | 1997-01-21 | The Lubrizol Corporation | Ashless, low phosphorus lubricant |
US6140457A (en) * | 1999-02-26 | 2000-10-31 | General Electric Company | Static-resistant polycarbonates having DI-t-alkylphenyl end groups |
US6680349B2 (en) * | 2000-08-31 | 2004-01-20 | Masao Sumita | Organohybrid-based damping material, method for producing the same, and damping improver for damping material |
US20080318814A1 (en) * | 2006-01-13 | 2008-12-25 | Albemarle Corporation | Lubricant Oil and Lubricating Oil Additive Concentrate Compositions |
US20100286004A1 (en) * | 2006-03-29 | 2010-11-11 | Albemarle Corporation | Lubricant oil additive compositions |
CN100575394C (en) * | 2007-04-27 | 2009-12-30 | 西安交通大学 | A kind of preparation method of hyper branched boric acid ester |
CN105503535A (en) * | 2015-08-03 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Mixed base catalyst catalysis-based bisphenol anti-oxidant preparation method and use |
CN105503535B (en) * | 2015-08-03 | 2017-08-11 | 中国科学院宁波材料技术与工程研究所 | The preparation method and application of bis-phenol kind antioxidant based on mixed base catalyst |
CN110591790A (en) * | 2019-07-23 | 2019-12-20 | 青岛博士德润滑科技有限公司 | Preparation method of environment-friendly copper corrosion inhibitor |
CN110591790B (en) * | 2019-07-23 | 2021-12-31 | 青岛博士德润滑科技有限公司 | Preparation method of environment-friendly copper corrosion inhibitor |
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